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Stereoselectivity in Reactions of Metal Complexes. Part X . Kinetics and stereoselectivity of the inner‐sphere electron‐transfer reaction between [Co(bamap)H 2 O] + (bamap = 2,6‐bis(3‐carboxy‐1,2‐dimethyl‐2‐azapropyl)pyridine) and optically active iron(II) complexes
Author(s) -
Bernauer Klaus,
Pousaz Philippe,
Porret Joelle,
Jeanguenat André
Publication year - 1988
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19880710545
Subject(s) - chemistry , stereoselectivity , kinetics , electron transfer , metal , crystallography , inner sphere electron transfer , stereochemistry , electron , catalysis , ion , organic chemistry , physics , quantum mechanics
Abstract The kinetics of the electron‐transfer reaction between racemic or optically active [Co(bamap)H 2 O] + and optically active Fe 2+ complexes of the three new pentadentate ligands bamap, alamp, and valmp has been investigated. All the reacting species show C 2 symmetry. With respect to aquo‐Fe 2+ , the reaction rate for the Fe 2+ complexes is enhanced by a factor of 10 4 to 10 5 , and the observed k ΔΛ / k ΛΛ ratio is 1.0, 1,9, and 1.2, respectively. In all cases where stereoselectivity is observed, the reaction is faster between the complexes of opposite absolute configuration ( ΔΛ or ΛΔ ) than between species with the same configuration ( ΛΛ or ΔΔ ). The stereoselectivity effects are discussed of the basis of the structure of the transition state and the interatomic distances between the two metal centers at the moment of electron transfer.